Generally, “zeolite” has been long a generic term of crystalline porous aluminosilicates and these are (SiO4)4− and (AlO4)5− having tetrahedral structures as the basic units of the structure. However, in recent years, it has been clarified that a structure peculiar or analogous to zeolite is present in other many oxides such as aluminophosphate.
International Zeolite Association (hereinafter simply referred to as “IZA”) describes the definition of zeolite in Atlas of Zeolite Structure Types, 5th edition, edited by W. Meier, D. H. Meier, D. H. Olson and Ch. Baerlocher, Elsevier (2001) (Non-Patent Document 1) (hereinafter simply referred to as “Atlas”). According to this definition, substances other than aluminosilicate having a similar structure are dealt with as an objective substance of which structure is to be specified, and these are called a zeolite-like material.
The details of the history thereof are particularly described in Yoshio Ono and Tateaki Yajima (compilers), Zeolite no Kagaku to Kogaku(Science and Engineering of Zeolite), pp. 1-13, published by Kodansha (Jul. 10, 2000) (Non-Patent Document 2).
The definition of “zeolite” as used in the present invention is based on the definition described in the above Yoshio Ono and Tateaki Yajima (compilers), Zeolite no Kagaku to Kogaku(Science and Engineering of Zeolite), pp. 1-13, published by Kodansha (Jul. 10, 2000) where zeolite includes not only aluminosilicate but also those having an analogous structure, such as titanosilicate.
In the present invention, a structure code composed of three alphabetical capital letters derived from the names of standard substances initially used for the clarification of structure, approved by IZA, is used for the structure of zeolite. This includes those recorded in Atlas and those approved in the fifth and later editions.
Further, unless otherwise indicated specifically, the “aluminosilicate” and “titanosilicate” as used in the present invention are not limited at all on the difference such as crystalline/non-crystalline or porous/non-porous and include “aluminosilicates” and “titanosilicates” in all properties.
The “molecular sieve” as used in the present invention is a substance having an activity, operation or function of sieving molecules by the size and includes zeolite. This is described in detail in “Molecular Sieve” of Hyojun Kagaku Yogo Jiten(Glossary for Standard Chemistry), compiled by Nippon Kagaku Kai, Maruzen (Mar. 30, 1991) (Non-Patent Document 3).
Recently, various studies have been made on the oxidation reaction of an organic compound using a titanosilicate, which is one of zeolites, as the catalyst and a peroxide as the oxidizing agent. Among titanosilicates, TS-1 as one of crystalline titanosilicates is used in various reactions after the synthesis method thereof is disclosed in U.S. Pat. No. 4,410,501 (Patent Document 1) and TS-1 is found to exhibit an activity in oxidation reactions using various peroxides. Specific examples thereof include a method disclosed in JP-B (“examined Japanese patent publication”,)-4-5028 (Patent Document 2) where TS-1 is used as the catalyst in epoxidation of an olefin compound using hydrogen peroxide or an organic peroxide as the oxidizing agent.
The structure code of TS-1 is MFI similarly to ZSM-5 which is a representative synthetic zeolite, and has an oxygen 10-membered ring. On the infrared absorption spectrum of TS-1 measured in the dehydrated state, an absorption band having a relative maximum value at 960 cm−1 is observed. The pore size is relatively small and 0.5 nm or less and therefore, the olefin compound which can be epoxidized is limited. Further, since the diffusion rate of the olefin compound as a reaction raw material into the inside of pores and the outflow rate of the product epoxy compound from pores are low, an industrially sufficient reaction activity can be hardly obtained. Moreover, a ring-opening reaction of the epoxy group takes place in the product epoxy compound, as a result, the selectivity disadvantageously decreases.
On the other hand, JP-A (“non-examined Japanese patent publication”)-7-242649 (Patent Document 3) discloses a method of epoxidating an olefin compound using a crystalline titanium-containing molecular sieve having a structure similar to aluminum-free zeolite beta (structure code: *BEA) as the catalyst and using hydrogen peroxide or an organic peroxide as the oxidizing agent.
On the infrared absorption spectrum of a crystalline titanium-containing molecular sieve having a structure similar to aluminum-free zeolite beta measured in the dehydrated state, an absorption band having a relative maximum value at 960 cm−1 is observed.
*BEA has a large pore size as compared with the structure code MFI of TS-1 and therefore, is expected to provide an effect of, for example, enabling a reaction of a compound having sterically high bulkiness or increasing the diffusion rate and thereby improving the reaction rate. Actually, the above-described patent publication discloses an example where a compound incapable of reacting by TS-1 can be oxidized. However, this oxidation reaction is disadvantageous in that the conversion of oxidizing agent is low in the case of using hydrogen peroxide as the oxidizing agent for the epoxidation reaction and since a ring-opening reaction of epoxide takes place to produce glycol, the selectivity decreases. Further, the molecular sieve described in that patent publication is high in the activity decreasing rate, in other words, short in the catalytic life and therefore, must be repeatedly subjected to a regeneration treatment on great occasions and this stands as a large obstacle to the implementation in an industrial scale.
On the other hand, in recent years, a synthetic zeolite having a structure code MWW different from MFI and *BEA is attracting an attention. The production process thereof is disclosed, for example, in JP-A-63-297210 (Patent Document 4).
Further, in Peng Wu, Takashi Tatsumi and Takayuki Komatsu, Chemistry Letters, 774 (2000) (Non-Patent Document 4), it is reported that a cyclohexene oxide can be produced by producing a crystalline titanosilicate containing a titanium atom in the crystal structure and having a structure code MWW and oxidizing cyclohexene using hydrogen peroxide and using the obtained crystalline titanosilicate as the catalyst. On the infrared absorption spectrum of the crystalline titanosilicate containing a titanium atom in the crystal structure and having a structure code MWW measured in the dehydrated state, an absorption band having a relative maximum value at 960 cm−1 is observed.
However, the yield of the objective is not sufficiently high, both epoxide and diol are produced in a fairly large amount, failing in exhibiting a tendency of selectively giving either one compound, and therefore, this technique has a problem for industrial use.
As such, although various proposals have been made on the oxidation reaction of an olefin compound using a titanosilicate as the catalyst and a peroxide as the oxidizing agent, the technique practicable in industry is limited and the olefin compound to which any of these techniques can be applied is very limited. A technique industrially applicable to many olefin compounds is not yet found.
(Patent Document 1)
U.S. Pat. No. 4,410,501
(Patent Document 2)
JP-B-4-5028
(Patent Document 3)
JP-A-7-242649
(Patent Document 4)
JP-A-63-297210
(Non-Patent Document 1)
Atlas of Zeolite Structure Types, 5th edition edited by W. Meier, D. H. Meier, D. H. Olson and Ch. Baerlocher, Elsevier (2001)
(Non-Patent Document 2)
Yoshio Ono and Tateaki Yajima (compilers), Zeolite no Kagaku to Kogaku (Science and Engineering of Zeolite), published by Kodansha (Jul. 10, 2000)
(Non-Patent Document 3)
Hyojun Kagaku Yogo Jiten (Glossary for Standard Chemistry), compiled by Nippon Kagaku Kai, Maruzen (Mar. 30, 1991)
(Non-Patent Document 4)
Peng Wu, Takashi Tatsumi and Takayuki Komatsu, Chemistry Letters, 774 (2000)